Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of trans-di­aqua­[2,5-bis­(pyridin-4-yl)-1,3,4-oxa­diazole]di­thio­cyanato­nickel(II)

Rhoufal, F.; Bentiss, F.; Guesmi, S.; Ketatni, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989019008727

Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of trans-diaqua[2,5-bis(pyridin-4-yl)-1,3,4-oxadiazole]dithiocyanatonickel(II)

F. Rhoufal, F. Bentiss, S. Guesmi, E. M. Ketatni, M. Saadi and L. El Ammari

The Ni^II atom in the mononuclear title complex has an almost regular octahedral N₄O₂ coordination geometry. In the crystal, the complex molecules are linked in a three-dimensional network through strong O—H

N hydrogen bonds.

Keywords: coordination complex; crystal structure; 1,3,4-oxadiazole; thiocyanate; spectroscopy; hydrogen bonds; Hirshfeld analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019008727/rz5259sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019008727/rz5259Isup2.hkl Contains datablock I

CCDC reference: 1911306

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Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.004 Å
R factor = 0.045
wR factor = 0.123
Data-to-parameter ratio = 22.5

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No syntax errors found



Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of        C13 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         13 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4 Note

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT012_ALERT_1_G N.O.K.   _shelx_res_checksum Found in CIF ......     Please Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni01     --N5       .        6.7 s.u.
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O1             102.8 Degree
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT794_ALERT_5_G Tentative Bond Valency for Ni01      (II)      .       2.08 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check


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Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Diaqua[2,5-bis(pyridin-4-yl)-1,3,4-oxadiazole]\ dithiocyanatonickel(II) top

Crystal data top

[Ni(NCS)₂(C₁₂H₈N₄O)₂(H₂O)₂]	F(000) = 676
M_r = 659.35	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5395 (7) Å	Cell parameters from 4425 reflections
b = 20.7595 (15) Å	θ = 2.5–30.5°
c = 8.6686 (6) Å	µ = 0.86 mm⁻¹
β = 108.908 (3)°	T = 296 K
V = 1453.81 (19) Å³	Block, green
Z = 2	0.36 × 0.27 × 0.20 mm

Data collection top

Bruker D8 VENTURE Super DUO diffractometer	4425 independent reflections
Radiation source: INCOATEC IµS micro-focus source	3100 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.041
Detector resolution: 10.4167 pixels mm^-1	θ_max = 30.5°, θ_min = 2.5°
φ and ω scans	h = −11→12
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −29→29
T_min = 0.638, T_max = 0.746	l = −12→12
19935 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0514P)² + 0.6622P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.69 e Å⁻³
4425 reflections	Δρ_min = −0.76 e Å⁻³
197 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.008 (2)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5151 (4)	0.85637 (12)	1.0739 (3)	0.0652 (8)
H1	0.560714	0.891631	1.037771	0.078*
C2	0.5764 (4)	0.79567 (10)	1.0599 (3)	0.0538 (6)
H2	0.662391	0.790140	1.017334	0.065*
C3	0.3276 (4)	0.81602 (14)	1.1842 (4)	0.0680 (8)
H3	0.242154	0.822966	1.226905	0.082*
C4	0.3778 (3)	0.75337 (12)	1.1741 (3)	0.0549 (6)
H4	0.327416	0.719031	1.208419	0.066*
C5	0.5052 (3)	0.74335 (10)	1.1116 (3)	0.0446 (5)
C6	0.5599 (3)	0.67774 (9)	1.0969 (3)	0.0411 (5)
C7	0.6815 (3)	0.60294 (9)	1.0151 (2)	0.0370 (4)
C8	0.7763 (3)	0.57441 (9)	0.9201 (3)	0.0375 (4)
C9	0.8891 (3)	0.61127 (10)	0.8754 (3)	0.0484 (6)
H9	0.916670	0.652504	0.917307	0.058*
C10	0.9594 (3)	0.58558 (10)	0.7675 (3)	0.0516 (6)
H10	1.035155	0.610562	0.737470	0.062*
C11	0.7456 (3)	0.51207 (9)	0.8619 (3)	0.0449 (5)
H11	0.674855	0.485395	0.894781	0.054*
C12	0.8219 (3)	0.49036 (9)	0.7543 (3)	0.0472 (6)
H12	0.800741	0.448454	0.715141	0.057*
C13	0.9838 (3)	0.64445 (9)	0.3751 (3)	0.0399 (5)
N1	0.3940 (3)	0.86677 (11)	1.1365 (3)	0.0707 (7)
N2	0.5248 (3)	0.62564 (9)	1.1590 (3)	0.0516 (5)
N3	0.6058 (3)	0.57608 (8)	1.1044 (2)	0.0478 (5)
N4	0.9250 (3)	0.52657 (8)	0.7032 (2)	0.0454 (5)
N5	0.9805 (3)	0.59299 (8)	0.4230 (3)	0.0478 (5)
O1	0.65795 (19)	0.66746 (6)	1.00419 (17)	0.0398 (3)
O2	0.7528 (2)	0.48479 (7)	0.3675 (2)	0.0575 (5)
H1W	0.703394	0.453575	0.366441	0.086*
H2W	0.708961	0.506891	0.292497	0.086*
S2	0.99004 (12)	0.71645 (3)	0.30546 (12)	0.0874 (3)
Ni1	1.000000	0.500000	0.500000	0.03858 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.084 (2)	0.0360 (11)	0.0605 (15)	0.0122 (12)	0.0024 (15)	−0.0055 (10)
C2	0.0703 (18)	0.0367 (10)	0.0498 (13)	0.0101 (11)	0.0131 (13)	−0.0037 (9)
C3	0.0566 (18)	0.0648 (17)	0.0704 (18)	0.0273 (14)	0.0038 (15)	−0.0176 (14)
C4	0.0494 (16)	0.0541 (13)	0.0537 (14)	0.0183 (11)	0.0063 (12)	−0.0082 (11)
C5	0.0505 (15)	0.0377 (10)	0.0386 (10)	0.0136 (9)	0.0047 (10)	−0.0048 (8)
C6	0.0467 (13)	0.0361 (10)	0.0389 (10)	0.0080 (9)	0.0116 (10)	−0.0038 (8)
C7	0.0407 (12)	0.0277 (8)	0.0410 (10)	0.0029 (7)	0.0112 (9)	0.0004 (7)
C8	0.0404 (12)	0.0301 (9)	0.0432 (10)	0.0021 (8)	0.0151 (10)	0.0000 (7)
C9	0.0549 (15)	0.0342 (9)	0.0616 (14)	−0.0117 (9)	0.0265 (13)	−0.0127 (9)
C10	0.0563 (16)	0.0392 (10)	0.0696 (15)	−0.0159 (10)	0.0346 (14)	−0.0113 (10)
C11	0.0537 (15)	0.0299 (9)	0.0595 (13)	−0.0042 (8)	0.0301 (12)	−0.0016 (8)
C12	0.0586 (16)	0.0287 (9)	0.0636 (14)	−0.0066 (9)	0.0325 (13)	−0.0062 (8)
C13	0.0403 (13)	0.0310 (9)	0.0456 (11)	−0.0011 (8)	0.0099 (10)	−0.0038 (8)
N1	0.0738 (18)	0.0484 (12)	0.0680 (14)	0.0283 (11)	−0.0071 (13)	−0.0148 (10)
N2	0.0647 (14)	0.0390 (9)	0.0609 (12)	0.0099 (9)	0.0340 (11)	0.0009 (8)
N3	0.0609 (14)	0.0330 (8)	0.0583 (11)	0.0063 (8)	0.0317 (11)	0.0018 (7)
N4	0.0526 (12)	0.0312 (8)	0.0620 (12)	−0.0059 (8)	0.0320 (10)	−0.0062 (8)
N5	0.0527 (13)	0.0311 (8)	0.0629 (12)	−0.0026 (7)	0.0234 (10)	−0.0001 (8)
O1	0.0500 (10)	0.0278 (6)	0.0421 (8)	0.0035 (6)	0.0159 (7)	−0.0007 (5)
O2	0.0481 (11)	0.0392 (8)	0.0786 (12)	−0.0102 (7)	0.0116 (9)	0.0160 (8)
S2	0.0959 (7)	0.0375 (3)	0.0972 (6)	−0.0107 (3)	−0.0123 (5)	0.0245 (3)
Ni1	0.0423 (3)	0.02354 (17)	0.0559 (3)	−0.00321 (14)	0.0241 (2)	−0.00040 (14)

Geometric parameters (Å, º) top

C1—N1	1.332 (4)	C8—C11	1.383 (3)
C1—C2	1.385 (3)	C9—C10	1.372 (3)
C1—H1	0.9300	C9—H9	0.9300
C2—C5	1.388 (3)	C10—N4	1.338 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—N1	1.325 (4)	C11—C12	1.375 (3)
C3—C4	1.381 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—N4	1.338 (3)
C4—C5	1.379 (3)	C12—H12	0.9300
C4—H4	0.9300	C13—N5	1.150 (3)
C5—C6	1.459 (3)	C13—S2	1.619 (2)
C6—N2	1.286 (3)	N2—N3	1.404 (2)
C6—O1	1.352 (3)	N4—Ni1	2.1327 (17)
C7—N3	1.285 (3)	N5—Ni1	2.0316 (18)
C7—O1	1.353 (2)	O2—Ni1	2.0748 (18)
C7—C8	1.456 (3)	O2—H1W	0.7715
C8—C9	1.380 (3)	O2—H2W	0.7846

N1—C1—C2	123.3 (3)	C8—C11—H11	120.7
N1—C1—H1	118.4	N4—C12—C11	123.21 (18)
C2—C1—H1	118.4	N4—C12—H12	118.4
C1—C2—C5	117.8 (3)	C11—C12—H12	118.4
C1—C2—H2	121.1	N5—C13—S2	179.0 (2)
C5—C2—H2	121.1	C3—N1—C1	117.8 (2)
N1—C3—C4	123.8 (3)	C6—N2—N3	105.56 (17)
N1—C3—H3	118.1	C7—N3—N2	106.48 (16)
C4—C3—H3	118.1	C12—N4—C10	117.08 (18)
C5—C4—C3	117.9 (3)	C12—N4—Ni1	122.28 (14)
C5—C4—H4	121.1	C10—N4—Ni1	119.80 (14)
C3—C4—H4	121.1	C13—N5—Ni1	172.93 (19)
C4—C5—C2	119.5 (2)	C6—O1—C7	102.77 (15)
C4—C5—C6	119.4 (2)	Ni1—O2—H1W	126.0
C2—C5—C6	121.1 (2)	Ni1—O2—H2W	119.7
N2—C6—O1	112.89 (17)	H1W—O2—H2W	111.7
N2—C6—C5	128.6 (2)	N5ⁱ—Ni1—N5	180.0
O1—C6—C5	118.47 (19)	N5ⁱ—Ni1—O2ⁱ	90.13 (7)
N3—C7—O1	112.30 (17)	N5—Ni1—O2ⁱ	89.87 (7)
N3—C7—C8	130.17 (17)	N5ⁱ—Ni1—O2	89.87 (7)
O1—C7—C8	117.41 (17)	N5—Ni1—O2	90.13 (7)
C9—C8—C11	118.93 (19)	O2ⁱ—Ni1—O2	180.00 (8)
C9—C8—C7	120.01 (17)	N5ⁱ—Ni1—N4	89.38 (7)
C11—C8—C7	120.85 (19)	N5—Ni1—N4	90.62 (7)
C10—C9—C8	118.35 (19)	O2ⁱ—Ni1—N4	91.57 (8)
C10—C9—H9	120.8	O2—Ni1—N4	88.43 (8)
C8—C9—H9	120.8	N5ⁱ—Ni1—N4ⁱ	90.62 (7)
N4—C10—C9	123.7 (2)	N5—Ni1—N4ⁱ	89.38 (7)
N4—C10—H10	118.2	O2ⁱ—Ni1—N4ⁱ	88.43 (8)
C9—C10—H10	118.2	O2—Ni1—N4ⁱ	91.57 (8)
C12—C11—C8	118.60 (19)	N4—Ni1—N4ⁱ	180.0
C12—C11—H11	120.7

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1W···N1ⁱⁱ	0.77	1.98	2.747 (2)	172
O2—H2W···N3ⁱⁱⁱ	0.78	2.14	2.918 (3)	173

Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) x, y, z−1.

Percentage contributions of intermolecular interactions to the Hirshfeld surface in [Ni(4-pox)₂(NCS)₂(H₂O)₂] top

Contact type	Percentage contribution
H···H	23.9
N···H/H···N	22.1
C···H/H···C	18.2
S···H/H···S	17.3
C···C	5.9
C···N/N···C	3.7
C···O/O···C	2.9
C···S/S···C	2.5
S···O/O···S	1.4
O···H/H···O	0.7
N···O/O···N	0.7
N···N	0.5

IR data (cm^-1) for the 4-pox ligand and the title complex [Ni(4-pox)₂(NCS)₂(H₂O)₂] top

Bond	4-pox	[Ni(4-pox)₂(NCS)₂(H₂O)₂]
C═C(pyridine)	1535–1414 (m)	1551–1418 (m)
C═N(pyridine)	1563 (m)	1569 (m)
C═N(oxadiazole)	1608 (m)	1618 (m)
C═N(thiocyanate)	–	2083 (s)
C—H	3040 (w)	3055 (w), 3084 (w)
O—H	–	3409 (m)

w = weak, m = medium, s = strong.

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Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of trans-di­aqua­[2,5-bis­(pyridin-4-yl)-1,3,4-oxa­diazole]di­thio­cyanato­nickel(II)

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of trans-diaqua[2,5-bis(pyridin-4-yl)-1,3,4-oxadiazole]dithiocyanatonickel(II)